Fuel detergent composed of hydropoly(oxyalkylene) oxyalkyl amine compound

ABSTRACT

A fuel oil detergent which efficiently constricts precipitate formation and octane number requirement increase in a carburetor, injector, and inlet system of an internal combustion engine, i.e., a hydropoly(oxyalkylene) oxyalkyl amine based compound, a process for preparing the compound, and a fuel oil composition including the compound.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on application No. 10-1999-0018908 filed inthe Korean Industrial Property Office on May 25, 1999, the content ofwhich is incorporated hereinto by reference.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to hydropolyoxyalkylene oxyalkyl aminecompounds useful as a novel fuel oil detergent, more particularly tohydropolyoxyalkylene oxyalkyl amine compounds useful as a novel fuel oildetergent, which can efficiently inhibit both the formation of depositsin the carburetor, injector and intake valve of internal combustionengines and octane number required value increases (ORI) byincorporating the active detergent into the fuel, and a process forpreparing the same and a fuel oil composition comprising the same.

(b) Description of the Related Art

It has been known that deposits are formed on the surface of injectors,intake valves, carburetors, etc., of internal combustion engines by theoxidation of the fuel and lubricant oil. These deposits formed in theintake valve block a mixed gas flow which enters a combustion chamber,thereby causing severe drive-ability problems such as misfire and pooracceleration and can significantly increase an automobile's fuelconsumption and produce harmful exhaust pollutants. Furthermore, thedeposits formed in a combustion chamber can create mechanical damage toa piston, piston ring, engine head, etc.

Conventionally, an aliphatic amine compound based on long-chainedhydrocarbons has been developed and used as a fuel oil detergent inorder to inhibit the formation of these deposits. It is disclosed inU.S. Pat. Nos. 3,438,757 and 3,574,576 that hydrocarbyl amines having amolecular weight of 425 to 10,000, preferably 450 to 5,000, are usefulas a fuel oil detergent or a lubricating oil dispersing agent ofinternal combustion engines. Furthermore, it is disclosed in EuropeanPatent No. 476,485 A that polybutylaminoalcohol prepared by reactingamine with polybutene epoxide obtained by epoxidizing polybutene isuseful as a detergent for the gasoline and as an additive to thelubricant oil. The polybutylaminoalcohol is produced by a nucleophilicsubstitution reaction of polybutene epoxide with amine.

However, there are problems in that the octane number required value ofan engine increases since the above detergents increase the formation ofdeposits in a combustion chamber, although they have effects ofinhibiting the formation of deposits on the surface of the intake valve.Deposits formed on the combustion chamber surface increase thetemperature of a combustion chamber by hindering heat transfer betweenan engine cooling system and the combustion chamber, provoking engineknock by inducing pre-ignition.

Furthermore, a high compression ratio occurs resulting in an engineknock since the volume of the combustion chamber is decreased whendeposits are formed on the surface of the combustion chamber. Knockingphenomena can cause damage to pistons, connecting rods, bearings, campushrods, etc., if it continues for a long period of time and (it cancause) energy inefficiency.

As described in the above, an octane number required value increasephenomena of an engine occurs when deposits are formed in the combustionchamber, and a fuel having a high octane number should be used so as toprevent the knocking phenomena from occurring in case of an enginehaving a high octane number required value increase. However, theknocking phenomena can be prevented without using a fuel having a highoctane number when the octane number required value increase of theengine is decreased by inhibiting or preventing the formation ofdeposits in the combustion chamber.

SUMMARY OF THE INVENTION

Therefore, it is an object of the present invention to provide ahydropolyoxyalkylene oxyalkyl amine compound as a novel fuel oildetergent which has superior intake valve cleaning effects and inhibitsor prevents octane number required value increases.

Furthermore, it is another object of the present invention to provide aprocess for preparing the hydropolyoxyalkylene oxyalkyl amine compounds.

In order to accomplish the above objects, the present invention providesa hydropolyoxyalkylene oxyalkyl amine compound as a novel fuel oildetergent.

Furthermore, the present invention provides a fuel oil concentratecomprising the hydropolyoxyalkylene oxyalkyl amine compound.

Furthermore, the present invention provides a fuel oil compositioncomprising the hydropolyoxyalkylene oxyalkyl amine compound and/orconcentrate.

Furthermore, the present invention provides a preparation process inwhich the hydropolyoxyalkylene oxyalkyl amine compound is prepared.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following detailed description, only the preferred embodiments ofthe invention have been shown and described, simply by way ofillustration of the best mode contemplated by the inventor(s) ofcarrying out the invention. As will be realized, the invention iscapable of modification in various obvious respects, all withoutdeparting from the invention. Accordingly, the description is to beregarded as illustrative in nature, and not restrictive.

The present invention is described in detail as follows.

As a hydropolyoxyalkylene oxyalkyl amine compound, a novel fuel oildetergent of the present invention has a structure such as the followingChemical Formula 1 of which the molecular weight is preferably from 200to 6,000.

where m is an integer from 1 to 10, preferably an integer from 1 to 2;

n is an integer from 1 to 80, preferably an integer from 1 to 50;

r and s, each of which can be the same or different, are eachindependently an integer from 0 to 10, preferably an integer from 0 to3;

R¹ is an alkyl derived from polyolefin having a molecular weight from200 to 5,000, preferably an alkyl derived from polyolefin having amolecular weight from 200 to 2,500;

R², R⁴, and R⁵, each of which can be the same or different, are eachindependently hydrogen or alkyl having 1 to 10 carbon atoms, preferablyalkyl having 1 to 2 carbon atoms;

R³, as a repetition unit of a polymer chain which can be the same ordifferent between repetition units, is alkylene having 2 to 10 carbonatoms, preferably alkylene having 2 to 5 carbon atoms;

R⁶ and R⁹, each of which can be the same or different, are eachindependently hydrocarbons comprising aromatic chains having 6 to 10carbon atoms or alkylenes having 2 to 10 carbon atoms, preferablyalkylenes having 2 to 6 carbon atoms; and

R⁷, R⁸, R¹⁰, and R¹¹, each of which can be the same or different, areeach independently hydrogen, hydrocarbons comprising aromatic chainshaving 6 to 10 carbon atoms, alkyls having 1 to 10 carbon atoms, orhydropolyoxyalkylene(oxyalkylene) of the following Chemical Formula 2:

R^(12—O) _(p) H

where p is an integer from 0 to 80, preferably an integer from 0 to 50;and

R¹², as a repetition unit of polymer chains which can be the same ordifferent between repetition units, is a hydrocarbon comprising aromaticchains having 6 to 10 carbon atoms or alkylenes having 2 to 10 carbonatoms, preferably alkylene having 2 to 5 carbon atoms.

A process for preparing a hydropolyoxyalkylene oxyalkyl amine basedcompound of the present invention consists of reacting hydroxyalkylamine of the following Chemical Formula 3 with alkyleneoxide having 2 to10 carbon atoms, preferably 2 to 5 carbon atoms:

where m is an integer from 1 to 10, preferably an integer from 1 to 2;

r and s, each of which can be the same or different, are eachindependently an integer from 0 to 10, preferably an integer from 0 to3;

R¹ is alkyl derived from polyolefin having a molecular weight from 200to 5,000, preferably alkyl derived from polyolefin having a molecularweight from 200 to 2,500;

R², R⁴, and R⁵, each of which can be the same or different, are eachindependently a hydrogen or alkyl having 1 to 10 carbon atoms,preferably alkyl having 1 to 2 carbon atoms;

R⁶ and R⁹, each of which can be the same or different, are eachindependently a hydrocarbon comprising aromatic chains having 6 to 10carbon atoms or alkylenes having 2 to 10 carbon atoms, preferablyalkylene having 2 to 6 carbon atoms; and

R¹³, R¹⁴, R¹⁵, and R¹⁶, each of which can be the same or different, areeach independently hydrogen, a hydrocarbon comprising aromatic chainshaving 6 to 10 carbon atoms, an alkyl having 1 to 10 carbon atoms, or anhydroxyalkyl of the following Chemical Formula 4:

—R^(17—OH)

where R¹⁷ is a hydrocarbon comprising aromatic chains having 6 to 10carbon atoms or alkylenes having 1 to 10 carbon atoms, preferablyalkylene having 1 to 5 carbon atoms.

Preparation of Hydroxyalkyl Amine

The first step reaction is epoxidation of polyolefin. Polyolefin havinga double bond forms oxirane rings by an oxidant which can causeepoxidation, thus becoming polyolefin epoxide. Polyolefin epoxide isprepared from polyolefin having an average molecular weight from 200 to5,000, preferably from 200 to 2,500.

Polyolefin, as a mixture of molecules having generally differentmolecular weights, can have one or more branched chains per 6 carbonatoms, preferably one or more branched chains per 4 carbon atoms, andpolyolefin having one or more branched chains per 2 carbon atoms is morepreferable. These polyolefins can be prepared from olefin having 2 to 6carbon atoms, preferably olefin having 3 to 4 carbon atoms, andisobutylene or polybutene prepared by reacting a C₄ distillatecontaining isobutylene is most preferable.

These polyolefins have double bonds, and they become polyolefin epoxidewhen these double bonds form oxirane rings with various oxidants.Oxidants which can be used in the preparation of polyolefin epoxide canbe all notified oxidants. Preferable oxidants include hydrogen peroxide,peracetic acid, perbenzoic acid, performic acid, monoperphthalic acid,percamphoric acid, persuccinic acid, pertrifluoroacetic acid, etc., andhydrogen peroxide is more preferable.

Where hydrogen peroxide is employed, an organic acid such as formic acidor acetic acid is additionally added. Particularly, in case of using anorganic acid having at least 2 carbon atoms such as acetic acid, it isdesirable to add an inorganic acid such as sulfuric acid or phosphoricacid. In this case, hydrogen peroxide is added with a molar ratio ofolefin to hydrogen peroxide being 1:0.2 to 1:3.0, preferably 1:0.4 to1:1.5. The reaction is slow when a molar ratio of olefin to hydrogenperoxide is below 1:0.2, and benefits are reduced when the molar ratioexceeds 1:3.0.

Organic acids are added with a molar ratio of olefin to organic acidbeing 1:0.1 to 1:1.5, preferably 1:0.2 to 1:1. The rate of reaction isslow when a molar ratio of olefin to organic acid is below 1:0.1, and aside reaction occurs in which ester is produced by the reaction ofproduced epoxide with organic acid when the molar ratio exceeds 1:1.5.

On the other hand, inorganic acids are added with a molar ratio ofolefin to inorganic acid is 1:0.1 to 1:0.6, preferably 1:0.2 to 1:0.4 incase of using organic acids having at least 2 carbon atoms includingacetic acid. The rate of reaction becomes slow when a molar ratio ofolefin to inorganic acid is below 1:0.1, and a side reaction occurs whenthe molar ratio exceeds 1:0.6.

The rate of reaction temperature is preferably from 20 to 90° C. Thereaction becomes slow when the reaction temperature is below 20° C., andhydrogen peroxide is decomposed resulting in preparation processdifficulties due to high temperature when it exceeds 90°.

The resulting products are washed with water to remove the oxidant andorganic acid, and then are distilled in a vacuum to remove the solventor are directly distilled in a vacuum without being washed, to obtainpolyolefin epoxide.

The second step is an isomerization reaction of the polyolefin epoxide.The polyolefin epoxide produced from the first step reaction has anoxirane ring which is opened by a strong base to form a double bond andto provide a hydroxy polyolefin. Such ring-opening reaction of thealkylene epoxide can also be found in the literature (e.g., Encyclopediaof Chemical Technology, 3^(rd) ed., vol 18, p 633).

In this reaction, common bases publicly known can be used. Preferably,an alkali metal alkoxide or an alkali metal hydroxide obtained by thereaction of an alcohol with alkali metals can be used. More preferably,sodium alkoxide, potassium alkoxide, sodium hydroxide or potassiumhydroxide can be used.

The molar ratio of the polyolefin epoxide to the base used in thereaction (with the base) is from 1:0.002 to 1:0.5, preferably from1:0.005 to 1:0.2. The reaction becomes slow when a molar ratio of thepolyolefin epoxide to the base is below 1:0.002, and an additionalprocess for removing bases remaining is needed when the molar ratioexceeds 1:0.5.

The reaction is carried out in 100˜300° C., preferably from 140 to 250°C. The rate of reaction becomes slow when the reaction temperature isbelow 100° C., and facility corrosion is caused by bases when it exceeds300° C.

Hydroxyl group substituted polyolefin is prepared after removingmetallic constituents in the resulting products by washing with water oradsorbing to cation exchange resin, etc. Excess amount of an alcoholiccomponent is distilled off at reduced pressure to providehydroxypolyolefin.

In the third step reaction, hydroxypolyolefin epoxide is prepared byexpoxidizing double bonds in hydroxypolyolefin prepared in the secondstep reaction in the same way as in the first step reaction.

On the other hand, one or more hydroxyl groups substituted polyolefinepoxide is produced when the second and third step reactions arerepeated, and two or more hydroxyl groups substituted polyalkenyl amine(one or more hydroxyl groups substituted polyalkenyl amine ishereinafter referred to as “hydroxyalkyl amine”) is produced when one ormore hydroxyl groups substituted polyolefin epoxide is reacted with thefourth step amine.

The fourth step reaction is the reaction of polyolefin epoxide preparedfrom the first step reaction or hydroxypolyolefin epoxide prepared fromthe third step reaction with amine. Polyolefin epoxide orhydroxypolyolefin epoxide can be represented in the following ChemicalFormula 5, and hydroxyalkyl amine is produced by the ring-openingreaction of polyolefin epoxide or hydropolyolefin epoxide and amines.Furthermore, the amine is represented in the following Chemical Formula6. One hydroxyl group exists as hydroxyalkyl amine prepared by omittingthe second and third step reactions and reacting polyolefin epoxideproduced from the first reaction with amine, and two or more hydroxylgroups exist as hydroxyalkyl amines produced by reactinghydroxypolyolefin epoxide with amine.

where m is an integer from 1 to 10, preferably an integer from 1 to 2;

R¹ is an alkyl derived from polyolefin having a molecular weight from200 to 5,000, preferably an alkyl derived from polyolefin having amolecular weight from 200 to 2,500; and

R², R⁴, and R⁵, each of which can be the same or different, are eachindependently hydrogen or alkyl having 1 to 10 carbon atoms, preferablyhydrogen or alkyl having 1 to 2 carbon atoms.

where R⁶ and R⁹, each of which can be the same or different, are eachindependently hydrocarbons comprising aromatic chains having 6 to 10carbon atoms or alkylenes having 2 to 10 carbon atoms, preferablyalkylenes having 2 to 6 carbon atoms; and

R¹³, R¹⁴, R¹⁵, and R¹⁶, each of which can be the same or different, areeach independently hydrogen, hydrocarbons comprising aromatic chainshaving 6 to 10 carbon atoms, alkyls having 1 to 10 carbon atoms, orhydroxyalkyl of the Chemical Formula 4.

Amines used to prepare hydroxypolyalkenyl amine compounds have one ormore basic nitrogen atoms with one or more hydrogen atoms, and theyinclude one or more compounds selected from the group consisting ofammonia, ethylenediamine, hexamethylenediamine, diethylenetriamine,triethylenetetraamine, di(trimethylene)triamine, dipropylenetriamine,tetraethylenepentaamine, 1,2-propylenediamine, 1,3-propylenediamine,dimethylaminopropylenediamine, dipropylenetriamine, 2-aminoethanol,2-(2-aminoethylamino)ethanol, 1-amino-2-propanol, 3-amino-i-propanol,4-aminophenol, N-methylamine, N-ethylamine, N-n-propylamine,N-isopropylamine, N-n-butylamine, N-isobutylamine, N-sec-butylamine,N-tert-butylamine, N-n-phentylamine, N-cyclophentylamine,N-n-hexylamine, N-cyclohexylamine, N,N-dimethylamine, N,N-diethylamine,N-di-n-propylamine, N,N-diisopropylamine, N,N-di-n-butylamine,N,N-diisobutylamine, N,N-di(2-hydroxyethyl)amine,N,N-di(3-hydroxypropyl)amine, N, N-di(ethoxyethyl)amine, N,N-di(propoxyethyl)amine, preferably ethylenediamine, diethylenetriamine,triethylenetetraamine or 2-aminoethanol.

The reaction of polyolefin epoxide, hydroxypolyolefin epoxide, or amixture thereof (hereinafter referred to as “polyolefin epoxide, etc.”)with the amine constituent is generally conducted at a temperature from100 to 280° C., preferably purely conducted or with solvents, at atemperature from 180 to 250° C. The rate of reaction becomes slow below100° C. of reaction temperature, and there are no further yield increaseeffects even when it exceeds 280° C. The reaction pressure is generallydetermined by reaction temperature, presence or absence of the solvent(whether or not solvents exist), and boiling point of the amineconstituent.

It is desirable that the molar ratio of the polyolefin epoxide to amineis from 1:1 to 1:10 and that a large quantity of amine is employed tosuppress desirably substituting a great deal of polyalkenyl groups forprotons of an amine. However, the reactor efficiency is dropped when themolar ratio exceeds 1:10.

The reaction of the polyolefin epoxide and the amine can be carried outin the presence of a catalyst in the state where oxygen does not exist.As a suitable catalyst, a Lewis acid such as trichloroaluminium,trifluoroboron, tetrachlorotitanium or ferric chloride, or a solidcatalyst containing a moiety of Lewis acid and Bronsted acid such asalumina, silica, silica alumina and also an organic acid and water, canbe used.

Furthermore, the reaction can be conducted with or without a reactionsolvent. The solvent is generally used when it is necessary to reducethe viscosity of the reaction product. The solvent if used should bestable and inactive to the reactants and the product. Preferablesolvents include aliphatic, aromatic hydrocarbon or aliphatic alcohols.

Reaction temperature can be varied according to whether or notpolyolefin epoxide, hydroxypolyolefin epoxide, amine or a catalyst isused. A reaction time is from 1 to 30 hours, preferably from 2 to 20hours.

When the reaction is completed, the reaction mixture is extracted with asolvent of hydrocarbon-water or hydrocarbon-alcohol-water to remove theresidual amine salt or un-reacted amine . The solvent is then distilledand removed under reduced pressure to separate possibly the product.Alternatively, the reaction mixture can be directly distilled off underreduced pressure to remove the residual amine and solvent.

Preparation of a Hydropolyoxyalkylene Oxyalkyl Amine Compound

A hydropolyoxyalkylene oxyalkyl amine compound of Chemical Formula 1used as a fuel oil detergent of the present invention is prepared by thereaction of hydroxyalkyl amines of Chemical Formula 3 withalkyleneoxides having 2 to 10 carbon atoms, preferably alkyleneoxideshaving 2 to 5 carbon atoms.

Alkyleneoxide polymerization is initiated from hydroxyl groups in ahydroxyalkyl amine of Chemical Formula 3 and partial primary orsecondary amine(s) with catalysts as in the general polyetherpreparation process by the initiation reaction of the hydroxy compound(R—OH) or amine compound (U.S. Pat. No. 2,841,479; U.S. Pat. No.2,782,240; and Kirk-Othmer “Encyclopedia of Chemical Technology”, vol.18, p616).

A homogeneous polymer like a hydropolyoxypropylene oxyalkyl amine isproduced when a single compound such as alkyleneoxide, for example onlyone type of the compound propyleneoxide, is used. However, a copolymeris easily obtained when a mixture of two or more types, for example amixture of propyleneoxide and butyleneoxide, is reacted with a hydroxycompound.

Furthermore, a random copolymer is obtained if reactivities of thealkyleneoxide used are each similar while a block copolymer is obtainedif a high reactive material such as ethyleneoxide becomes a copolymer.In case of preparing a block copolymer, generally a hydroxy compound isreacted first with alkyleneoxide, and again with another alkyleneoxide,repeatedly.

A hydropolyoxyalkylene oxyalkyl amine compound can be prepared byreacting hydroxyalkyl amine with one or more compounds selected from thegroup consisting of alkyleneoxides having 2 to 10 carbon atoms,preferably one or more compounds selected from the group consisting ofalkyleneoxides having 2 to 5 carbon atoms. Therefore, ahydropolyoxyalkylene chain in a hydropolyoxyalkylene oxyalkyl aminecompound of the present invention can be a homogeneous polymer ofalkyleneoxide, a random copolymer, or a block copolymer.

Catalysts which are used to prepare a hydropolyoxyalkylene oxyalkylamine compound include alkaline metal compounds or alkali earth metalcompounds, preferably potassium hydroxide, sodium hydroxide, potassium,potassium alkoxide or sodium alkoxide, more preferably potassiumhydroxide and sodium hydroxide.

The reaction of hydroxyalkyl amines and alkyleneoxides is conductedwithout oxygen and with catalysts at a temperature from 60 to 200° C.,preferably purely conducted or under the existence of solvents, at atemperature from 80 to 150° C. The rate of reaction becomes slow whenthe reaction temperature is below 60° C. while a side reaction occurswhen it exceeds 200° C. The reaction pressure is different according toboiling points of solvents or alkyleneoxide used, and depends on thesolvent and alkyleneoxide constituents having a low boiling point.

A somewhat yellow colored hydropolyoxyalkylene oxyalkyl amine compoundcan be obtained by removing catalysts using adsorbent or ion exchangeresin or washing with water and removing unreacted alkyleneoxide andsolvents with reduced pressure distillation after the termination ofreaction.

Fuel Oil Detergent Concentrate and Fuel Oil Detergent Composition

A fuel detergent of the present invention is used by adding it tohydrocarbon fuels so as to effectively inhibit both the formation ofdeposits in carburetors, injectors and inlet systems of internalcombustion engines as well as octane number required value increases.Concentration of a detergent for maintaining engine cleanliness isdetermined depending on fuel type, engine type and whether or not otherfuel additives exist.

Generally, a hydropolyoxyalkylene oxyalkyl amine compound used as a fueloil detergent of the present invention is used in a hydrocarbon fuel ina concentration from 50 to 5,000 ppm by weight, preferably in aconcentration from 100 to 3,000 ppm by weight. Cleaning effects areminor when the concentration is below 50 ppm by weight while synergyeffects of increased addition do not exist when it exceeds 5,000 ppm byweight. A boiling point of a hydrocarbon fuel is preferably between aboiling point of gasoline and that of diesel.

The detergent of the present invention may be formulated as aconcentrate, using an inert stable oleophillic organic solvent having aboliling point from about 65 to 205° C. Preferably, aliphatic oraromatic hydrocarbon solvents can be used as a solvent in a fuel oildetergent concentrate, and benzene, toluene, xylene, or an aromaticmaterial having a higher boiling point than benzene can be used as thearomatic solvent.

The amount of the detergent constituent hydropolyoxyalkylene oxyalkylamine compound in the concentrate is from 10 to 90% by weight,preferably from 30 to 80% by weight. Concentration effects are difficultto be expected when the content is below 10% by weight while it isdifficult to transfer products due to viscosity increase when it exceeds90% by weight.

A fuel oil detergent of the present invention can be used in the fueltogether with other kinds of ususal additives. Octane number improversuch as MTBE, antioxidants, antiknocking agents, a demulsifier, etc.,can be used together in gasoline fuel, and they can be used in dieselfuel together with other notified additives such as a pour pointdepressnat, a flow improver, a cetane number improver, etc.

A fuel oil detergent of the present invention can be employed with afuel-soluble nonvolatile carrier oil. Such a carrier oil can be selectedfrom a poly(oxyalkylene) derivative, a mineral oil, polyalkene, etc. Thecarrier oil is considered as to support the inhibition of the formationof deposits when used together with a detergent for the fuel, and canprovide a synergistic effect to inhibit the formation of deposits whenused together with the fuel detergent of the present invention. Thecarrier oil is added generally in the amount of 100 to 5,000 ppm byweight, preferably 200˜2,000 ppm by weight relative to the hydrocarbonfuel. The liquid carrier oil can be used additively with the fueldetergent concentrate in the amount of 20˜60% by weight, preferably30˜50% by weight.

The present invention is described more in detail as follows.

The following EXAMPLES are only for exemplifying the present invention,but the present invention is not limited to the EXAMPLES.

PREPARATION EXAMPLE 1 Preparation of Polybutene Epoxide

200 g of polybutene (Daelim polybutene PB-900, molecular weight 920),100 g of xylene, and 10.2 g of formic acid were introduced into a 500 mlflask equipped with a condenser, and agitated. 15 g of 60% hydrogenperoxide was added through an injection pump for one hour whilemaintaining a temperature in the flask at 50° C. and the reactants werereacted for 4 hours.

After separating the aqueous layer in the mixture using a 1,000 mlseparating funnel when the epoxidation reaction was completed, thesolvent of the organic layer was distilled off under a reduced pressureto obtain 195 g of slightly yellowish polybutene epoxide. The formationof epoxide was confirmed by nuclear magnetic resonance (NMR) detection.The yield of the polybutene epoxide was 96% by weight. When theresultant product was subjected to a column chromatography on silicagel, the un-reacted polybutene was eluted by n-hexane. The yield of thepolybutene epoxide can be determined by measuring the weight of theeluted portion after distilling off the n-hexane.

PREPARATION EXAMPLE 2 Preparation of Polybutene Epoxide

When polybutene epoxide was prepared using 200 g of polybutene (Daelimpolybutene PB-680, molecular weight 680), 100 g of xylene, 13.5 g offormic acid, and 20 g of 60% hydrogen peroxide in the same method as inPREPARATION EXAMPLE 1, the yield was 97% by weight.

PREPARATION EXAMPLE 3 Preparation of Polybutene Epoxide

When polybutene epoxide was prepared using 253 g of polybutene (Daelimpolybutene PB-450, molecular weight 450), 100 g of heptane, 25.8 g offormic acid, and 38 g of 60% hydrogen peroxide in the same method as inPREPARATION EXAMPLE 1, the yield was 91% by weight.

PREPARATION EXAMPLE 4 Preparation of Hydroxypolybutene

130 g of polybutene epoxide prepared in the PREPARATION EXAMPLE 1 and asolution in which 0.8 g of potassium hydroxide were dissolved into 40 gof isopropyl alcohol were introduced into a high pressure reactor to bereacted under nitrogen atmosphere at 200° C. for 3 hours. When thereaction was completed, the reaction mixture was introduced into a 500ml liquid separating funnel and then 200 ml of petroleum ether was addedto the funnel. The mixture was washed with 200 ml of water twice toremove potassium.

The reaction mixture completely washed was distilled to remove alcoholand the solvent under reduced pressure, 128 g of yellowhydroxypolybutene was obtained. The formation of the hydroxypolybutenewas recognized through the detection of a double bond by NMR and hydroxygroup by FT-IR. The hydroxyl value in the resultant product was 39.

PREPARATION EXAMPLE 5 Preparation of Hydroxypolybutene

Hydroxypolybutene was prepared in the same method as in the PREPARATIONEXAMPLE 4 using polybutene epoxide prepared in the PREPARATION EXAMPLE2, and the hydroxyl value of the resultant product was 48.4.

PREPARATION EXAMPLE 6 Preparation of Hydroxypolybutene Epoxide

Hydroxypolybutene epoxide was prepared by reacting 100 g ofhydroxypolybutene prepared in the PREPARATION EXAMPLE 4, 50 g of xylene,5 g of formic acid, and 9 g of 60% hydrogen peroxide in the same methodas in the PREPARATION EXAMPLE 1. The formation of hydroxypolybuteneepoxide could be confirmed by NMR analysis, and the yield of the epoxidewas 94%.

PREPARATION EXAMPLE 7 Preparation of Hydroxypolybutene Epoxide

Hydroxypolybutene epoxide was prepared using hydroxypolybutene preparedin the PREPARATION EXAMPLE 5 in the same method as in the PREPARATIONEXAMPLE 6, the yield of the epoxide was 94%.

PREPARATION EXAMPLE 8 Preparation of Dihydroxypolybutenyl Amine

80 g of hydroxypolybutene epoxide prepared in the PREPARATION EXAMPLE 6,30 g of diethyltriamine, and 3 g of water were introduced into a highpressure reactor and reacted under nitrogen atmosphere at 230° C. for 4hours. Dihydroxy polybutenyl amine was obtained by removing unreactedamine at 200° C. and 100 torr for one hour with a reduced pressuredistillation method while generating nitrogen bubbles after the reactiontermination.

The amount of polybutene-derived amine compound in the resultant productwas determined by column chromatography on silica gel. Elution withn-hexane/diethylether(1:1, v/v) gave the un-reacted polybutene andderivatives thereof which were not combined to the amine. The amount ofthe polybutene-derived amine compounds can be determined by measuringthe weight of the residual portion after distilling off the n-hexane anddiethylether.

As the results of analysis, the amount of polybutene-derived aminecompound was 50% by weight and that of basic nitrogen was 1.75% ofweight in the resultant product, and the hydroxyl value was 61.

PREPARATION EXAMPLE 9 Preparation of Dihydroxypolybutenyl Amine

Dihydroxypolybutenyl amine was prepared in the same method as inPREPARATION EXAMPLE 8 using 80 g of hydroxypolybutene epoxide preparedin the PREPARATION EXAMPLE 7, 40 g of diethylenetriamine, and 4 g ofwater. The amount of the polybutene-derived amine compound in theresultant product was 63% by weight and that of basic nitrogen was 2.95%by weight, and the hydroxyl value was 63.

PREPARATION EXAMPLE 10 Preparation of Hydroxyalkyl Amine

80 g of polybutene epoxide prepared in the PREPARATION EXAMPLE 1 and 30g of diethylenetriamine were introduced into a high pressure reactor andreacted at 230° C. for 20 hours in the same method as in PREPARATIONEXAMPLE 8, thereby preparing hydroxyalkyl amine. The amount ofhydroxyalkyl amine compound in the resultant prodcut was 42% by weightand that of basic nitrogen was 1.51% by weight.

PREPARATION EXAMPLE 11 Preparation of Hydroxyalkyl Amine

80 g of polybutene epoxide prepared in the PREPARATION EXAMPLE 2, 43 gof ethanolamine, and 4.3 g of water were introduced into a high pressurereactor and reacted at 230° C. for 20 hours in the same method as inPREPARATION EXAMPLE 8, thereby preparing hydroxyalkyl amine.

The amount of hydroxyalkyl amine compound in the resultant product was42% by weight and that of basic nitrogen was 0.849% by weight.

PREPARATION EXAMPLE 12 Preparation of Hydroxyalkyl Amine

80 g of polybutene epoxide prepared in the PREPARATION EXAMPLE 2, 110 gof diethylenetriamine, and 12 g of water were introduced into a highpressure reactor and reacted at 230° C. for 3 hours in the same methodas in PREPARATION EXAMPLE 8, thereby preparing hydroxyalkyl amine.

The amount of hydroxyalkyl amine compound in the resultant product was42% by weight and that of basic nitrogen was 2.122% by weight.

PREPARATION EXAMPLE 13 Preparation of Hydroxyalkyl Amine

80 g of polybutene epoxide prepared in the PREPARATION EXAMPLE 3, 63 gof diethylenetriamine, and 3.3 g of water were introduced into a highpressure reactor and reacted at 230° C. for 4 hours in the same methodas in PREPARATION EXAMPLE 8, thereby preparing hydroxyalkyl amine.

The amount of hydroxyalkyl amine compound in the resultant product was46% by weight and that of basic oxygen was 3.276% by weight.

PREPARATION EXAMPLE 14 Preparation of Hydropolyoxypropylene OxyalkylAmine

After introducing 60 g of dihydroxypolybutenyl amine prepared in thePREPARATION EXAMPLE 8 and 7.15 g of 5% by weight potassium hydroxideisopropyl alcohol solution into a 300 ml high pressure reactor,isopropyl alcohol was removed from the reactor at 120° C. for 30 minuteswhile generating nitrogen bubbles at a rate of 600 ml/min, and the restof the isopropyl alcohol was removed with reduced pressure distillationat 120° C. and 100 torr for 30 minutes. After lowering the isopropylalcohol removed reactor to room temperature and adding 83 g of propyleneoxide, it was reacted while increasing the reactor temperature to 120°C. The reactor temperature reached 120° C., and the reaction wasterminated after 69 minutes.

After terminating the reaction, the reactor temperature was lowered toroom temperature. And then, the reaction mixture was dissolved by adding200 ml of normal-hexane, put into a 500 ml separating funnel, and washedtwice with 200 ml of water thereby removing the potassium constituent.

Slightly yellowish hydropolyoxypropylene oxyalkyl amine compound wasobtained by removing unreacted propylene oxide or normal-hexane in thepotassium constituent removed reaction mixture with a reduced pressuredistillation method at 130°.

The amount of basic nitrogen in the prepared hydropolyoxypropyleneoxyalkyl amine was 0.905% by weight.

PREPARATION EXAMPLE 15 Preparation of Hydropolyoxypropylene OxyalkylAmine

A hydropolyoxypropylene oxyalkyl amine compound was prepared in the samemethod as in the PREPARATION EXAMPLE 14 using 60 g ofdihydroxypolybutenyl amine prepared in the PREPARATION EXAMPLE 9 and4.05 g of 5% potassium hydroxide isopropyl alcohol solution. The reactortemperature reached 120° C. in 50 minutes after the temperature startedrising, and the reaction was terminated after 65 minutes.

The amount of basic nitrogen in the prepared hydropolyoxypropyleneoxyalkyl amine was 1.75% by weight.

PREPARATION EXAMPLE 16 Preparation of Hydropolyoxypropylene OxyalkylAmine

A hydropolyoxypropylene oxyalkyl amine compound was prepared in the samemethod as in PREPARATION EXAMPLE 14 after putting 60 g of hydroxyalkylamine prepared in the PREPARATION EXAMPLE 10, 7.15 g of 5% potassiumhydroxide isopropyl alcohol solution, and 50 g of normal-hexane into a300 ml high pressure reactor. The reactor temperature reached 120° C. in50 minutes after the temperature started rising, and the reaction wasterminated after 60 minutes.

The amount of basic nitrogen in the prepared hydropolyoxypropyleneoxyalkyl amine compound was 0.780% by weight.

PREPARATION EXAMPLE 17 Preparation of Hydropolyoxypropylene OxyalkylAmine

80 g of hydroxyalkyl amine prepared in the PREPARATION EXAMPLE 11, 98 gof propylene oxide, and 0.223 g of 95% potassium hydroxide were put intoa 300 ml high pressure reactor and reacted while raising the reactortemperature to 120° C. The reactor temperature reached 120° C. in 60minutes after the temperature started rising, and the reaction wasterminated after 120 minutes.

A slightly yellowish hydropolyoxypropylene oxyalkyl amine compound wasobtained by treating the reaction mixture in the same method as in thePREPARATION EXAMPLE 14 after the reaction termination.

The amount of basic nitrogen in the prepared hydropolyoxypropyleneoxyalkyl amine compound was 0.695% by weight.

PREPARATION EXAMPLE 18 Preparation of Hydropolyoxypropylene OxyalkylAmine

80 g of hydroxyalkyl amine prepared in the PREPARATION EXAMPLE 12, 68 gof propylene oxide, and 0.260 g of 95% potassium hydroxide wereintroduced into a 300° high pressure reactor and reacted while raisingthe reactor temperature to 130° C. The reactor temperature reached 130°in 120 minutes after the temperature started rising, and the reactionwas terminated after 220 minutes.

A slightly yellowish hydropolyoxypropylene oxyalkyl amine compound wasobtained by treating the reaction mixture in the same method as in thePREPARATION EXAMPLE 14 after the reaction termination.

The amount of basic nitrogen in the prepared hydropolyoxyalkyleneoxyalkyl amine hydroxyalkylamine compound was 1.309% by weight.

PREPARATION EXAMPLE 19 Preparation of Hydropolyoxypropylene OxyalkylAmine

A hydropolyoxypropylene oxyalkyl amine was prepared in the same methodas in the PREPARATION EXAMPLE 14 after introducing 60 g of hydroxyalkylamine prepared in the PREPARATION EXAMPLE 12 and 4.20 g of 5% potassiumhydroxide isopropyl alcohol solution into a 300 ml high pressurereactor. The reactor temperature reached 120° C. in 50 minutes after thetemperature started rising, and the reaction was terminated after 60minutes. The amount of basic nitrogen in the preparedhydropolyoxypropylene oxyalkyl amine was 1.297% by weight.

PREPARATION EXAMPLE 20 Preparation of Hydropolyoxypropylene OxyalkylAmine

60 g of hydroxyalkyl amine prepared in the PREPARATION EXAMPLE 13 and apotassium isopropoxide solution prepared by dissolving 0.234 g ofpotassium metal into isopropyl alcohol were introduced into a 300 mlhigh pressure reactor and the reactant mixture was distilled for 30minutes to remove isopropylalcohol under reduced pressure to 100 torr at120° C., for 30 minutes. After lowering the isopropyl alcohol removedreactor to room temperature and adding 101 g of propylene oxide, it wasreacted while increasing the reactor temperature to 120° C. The reactortemperature reached 120° C. in 70 minutes after the temperature beganrising, and the reaction was terminated after 190 minutes.

A slightly yellowish hydropolyoxypropylene oxyalkyl amine compound wasobtained by treating the reaction mixture in the same method as in thePREPARATION EXAMPLE 14 after finishing the reaction. The amount of basicnitrogen in the prepared hydropolyoxypropylene oxyalkyl amine compoundwas 1.910% by weight.

Intake Valve Deposit Test of the Gasoline Engine (Sample Selection Test)

An intake valve deposit test was carried out in a simulator made byToyota Company in Japan. The simulator is designed so that thetemperature of the valve is controlled by an electric heater and flowrate of the oil ejected through the valve guide to the surface of thevalve is also controlled. Thus, the simulator is known as adequateequipment for the intake valve deposit test (SAE Technical paper series900152, “Mechanism of intake valve deposit formation part 2: simulationtest”, SAE Technical paper series 922265, “Mechanism of intake valvedeposit formation part III: Effects of gasoline quality”).

The test was undertaken for 10 hours in the conditions as in thefollowing Table 1.

TABLE 1 Test hour 10 hours Injection rate of the fuel 100 ml/hr Flowrate of the oil 0.035 to 0.045 ml/hr Valve speed 500 rpm Test cycle(Temperature of valve) 160° C. (0.5 hr) 250° C. (0.5 hr)

After an intake valve was separated from an engine, washed withnormal-heptane, and dried, its weight was measured in 0.01 mg units, andit was then reinstalled for conducting the test. After the 10 hour test,deposits on the bottom surface were removed after separating the valve.After removing materials dissolved in normal-heptane by washing withnormal-heptane and drying, the weight was measured. At this time, thedifference of valve weight between before and after the test was takenas the weight of the deposit formed for the test.

EXAMPLE 1 Intake Valve Deposit Test of the Gasoline Engine

The intake valve deposit test was undertaken in the same method as inthe above after preparing a fuel oil concentrate by mixing ahydropolyoxypropylene oxyalkyl amine compound prepared in thePREPARATION EXAMPLE 15 with xylene in an amount of 50% by weight andadding 400 ppm by weight of fuel oil concentrate to commercial unleadedgasoline which did not contain a detergent.

EXAMPLE 2 Intake Valve Deposit Test of the Gasoline Engine

The intake valve deposit test was undertaken in the same method as inthe EXAMPLE 1 using a hydropolyoxypropylene oxyalkyl amine compoundprepared in the PREPARATION EXAMPLE 17.

COMPARATIVE EXAMPLE 1 Intake Valve Deposit of the Gasoline Engine

The intake valve deposit test was undertaken in the same method as inthe EXAMPLE 1 using a hydroxyamine compound prepared in the PREPARATIONEXAMPLE 10.

COMPARATIVE EXAMPLE 2 Intake Valve Deposit of the Gasoline Engine

The intake valve deposit test was undertaken in the same method as inthe EXAMPLE 1 by adding 400 ppm by weight of commercial gasolinedetergent to a commercial unleaded gasoline which did not contain adetergent.

COMPARATIVE EXAMPLE 3 Intake Valve Deposit of the Gasoline Engine

The intake valve deposit test was undertaken in the same method as inthe EXAMPLE 1 using commercial unleaded gasoline which did not contain adetergent.

The amount of deposit formed on the intake valve in shown in Table 2.

TABLE 2 Test Deposits on intake Valve (mg/valve) EXAMPLE 1 0.55 EXAMPLE2 0.42 COMPARATIVE EXAMPLE 1 0.61 COMPARATIVE EXAMPLE 2 0.67 COMPARATIVEEXAMPLE 3 20.12

A detergent of the present invention had superior inhibiting effects ofthe production of intake valve deposits as shown in the above Table 2.

The Intake Valve Deposit and Combustion Chamber Deposit Test of GasolineEngine

The intake valve deposit and combustion chamber deposit test of thegasoline engine was undertaken on Hyundai Motor Company's Elantra engine1.6 l DOHC and its specifications are represented in the following Table3.

TABLE 3 126/6000 Type of Engine DOHC 4 cylinder Maximum Output (PS/rpm)Bore × stroke 82.3 × 75 mm Maximum Torque 15.3/5000 (kg/rpm)Displacement Volume 1,596 cc Fuel Injection MPI Type Compression Ratio9.2 Maximum Speed 180 km/hr

The test mode used was a Benz M102E, and its test conditions arerepresented in the following Table 4.

TABLE 4 Test Hour 60 hours Torque 3.1 to 3.7 Nm Oil Temperature 90 to105° C. Inlet temperature 25 to 35° C. Cooling Water 85 to 95° C. Rpm800 to 3,000 Temperature

After an intake valve was separated from an engine, washed withnormal-heptane, and dried, its weight was measured in 0.01 mg units, andit was then reinstalled for conducting the test. After the 60 hour test,deposits on the bottom surface were removed after separating the valve.After removing materials dissolved in normal-heptane by washing withnormal-heptane and drying, the weight was measured. At this time, thedifference of valve weight between before and after the test was takenas the weight of the deposit formed for the test.

EXAMPLE 3 The Intake Valve Deposit and Combustion Chamber Deposit Testof Gasoline Engine

The intake valve deposit and combustion chamber deposit test wasundertaken in the same method as in the above after preparing a fuel oilconcentrate by mixing a hydropolyoxypropylene oxyalkyl amine compoundprepared in the PREPARATION EXAMPLE 15 with xylene in an amount of 50%by weight and adding 600 ppm by weight of fuel oil concentrate tocommercial unleaded gasoline which did not contain a detergent.

COMPARATIVE EXAMPLE 4 The Intake Vvalve Deposit and Combustion ChamberDeposit Test of Gasoline Engine

The intake valve deposit and combustion chamber deposit test wasundertaken in the same method as in the EXAMPLE 3 after preparing a fueloil concentrate by mixing a hydroxyalkyl amine compound prepared in thePREPARATION EXAMPLE 10 with xylene in an amount of 50% by weight andadding 400 ppm by weight of fuel oil concentrate to commercial unleadedgasoline which did not contain a detergent.

COMPARATIVE EXAMPLE 5 The Intake Valve Deposit and Combustion ChamberDeposit Test of Gasoline Engine

The intake valve deposit and combustion chamber deposit test wasundertaken in the same method as in the EXAMPLE 3 using commercialunleaded gasoline which did not contain a detergent.

After the test, an intake valve and combustion chamber precipitateproduction amount was determined and it is represented in the followingTable 5.

TABLE 5 Addition Deposits on Deposits in the combustion amount intakechamber (/ΔII) (ppm by Valve Piston Cylinder Test weight) (mg/valve)crown head EXAMPLE 3 600 5.5 90.6 86.2 COMPARATIVE 400 5.6 99.2 102.4EXAMPLE 4 COMPARATIVE 0 137.6 66.2 79.5 EXAMPLE 5

In case of adding a detergent of the present invention to a gasolinefuel, a much lesser amount of intake valve deposits were produced ascompared with a non additive fuel (Comparative Example 5) in which adetergent was not added, and a similar amount of intake valve depositsas compared with conventional detergent added gasoline was produced.

However, deposits formed in the combustion chamber were decreased incomparison with the gasoline containing the concentrate of ComparativeExamples. This shows that the detergent of the present invention has anexcellent detergency for the intake valves and combustion chambers ofgasoline engines.

As described in the above, the amount of the intake valve deposits ofmotors was remarkably decreased and that of the combustion chamberdeposits was also decreased as compared to existing detergents(Comparative Example 4) in case of adding a fuel detergent of thepresent invention to a gasoline fuel. Therefore, motor drivingperformance is improved, amounts of harmful exhaust gas are decreased,and breakdowns can be prevented in case of adding a fuel detergent ofthe present invention to a gasoline fuel.

While the present invention has been described in detail with referenceto the preferred embodiments, those skilled in the art will appreciatethat various modifications and substitutions can be made thereto withoutdeparting from the spirit and scope of the present invention as setforth in the appended claims.

What is claimed is:
 1. A hydropolyoxyalkylene oxyalkyl amine compoundrepresented in the following Chemical Formula 1 as a fuel oil detergent:

where m is an integer from 1 to 10; n is an integer from 1 to 80; r ands, each of which can be the same or different, are each independently aninteger from 0 to 10; R¹ is an alkyl derived from a polyolefin having amolecular weight from 200 to 5,000; R², R⁴, and R⁵, each of which can bethe same or different, are each independently hydrogen or an alkylhaving 1 to 10 carbon atoms; R³, as a repetition unit of polymer chainswhich can be the same or different between repetition units, is analkylene having 2 to 10 carbon atoms; R⁶ and R⁹, each of which can bethe same or different, are each independently hydrocarbons selected fromaromatic chains having 6 to 10 carbon atoms or alkylenes having 2 to 10carbon atoms; and R⁷, R⁸, R¹⁰, and R¹¹, each of which can be the same ordifferent, are each independently hydrogen, hydrocarbons selected fromaromatic chains having 6 to 10 carbon atoms, alkyls having 1 to 10carbon atoms, or hydropolyoxyalkylene of the following Chemical Formula2:  R¹²—OH  [Chemical Formula 2] where p is an integer from 0 to 80;and R¹², as a repetition unit of a polymer chain which can be the sameor different between repetition units, is a hydrocarbon selected fromaromatic chains having 6 to 10 carbon atoms or alkylene having 2 to 10carbon atoms.
 2. A hydropolyoxyalkylene oxyalkyl amine compound inaccordance with claim 1, wherein R¹ of the Chemical Formula 1 is analkyl derived from a polyolefin which is prepared from isobutylene or aC₄ distillate containing isobutylene.
 3. A hvdropolyoxyalkylene oxyalkylamine compound in accordance with claim 2, wherein the polyolefinmolecular weight is from 200 to 2,500.
 4. A hydropolyoxyalkyleneoxyalkyl amine compound in accordance with claim 1, wherein R³, R⁶, R⁹,and R¹² of the Chemical Formula 1, each of which can be the same ordifferent, are each independently an alkylene having 2 to 5 carbonatoms.
 5. A hydropolyoxyalkylene oxyalkyi amine based fuel oilconcentrate, wherein 10 to 80% by weight of the hydropolyoxyalkyleneoxyalkyl amine compound of claim 1 is contained in an aliphatic oraromatic organic solvent, of which the boiling point is in a range from65 to 205 ° C.
 6. A hydrocarbon fuel oil composition comprising ahydropolyoxyalkylene oxyalkyl amine compound of claim
 1. 7. Ahydrocarbon fuel oil composition in accordance with claim 6, wherein theboiling point of the hydrocarbon fuel oil composition is in a rangebetween a boiling point of gasoline and that of diesel fuel.
 8. Ahydrocarbon fuel oil composition in accordance with claim 6, wherein thehydrocarbon fuel oil composition comprises 50 to 5,000 ppm by weight ofthe hydropolyoxyalkylene oxyalkyl amine compound of claim
 1. 9. Aprocess for preparing a hydropolyoxyalkylene oxyalkyl amine compound,wherein the hydropolyoxyalkylene oxyalkyl amine compound of claim 1 isprepared by reacbng hydroxyalkyl amine represented as in the followingChemical Formula 3 with alkyleneoxide having 2 to 10 carbon atoms undercatalysts of alkali metal compounds:

where m is an integer from 1 to 10; r and s, each of which can be thesame or different, are each independently an integer from 0 to 10; R¹ isan alkyl derived from a polyolefin having a molecular weight from 200 to5,000; R², R⁴, and R⁵, each of which can be the same or different, areeach independently hydrogen or an alkyl having 1 to 10 carbon atoms; R⁶and R⁹, each of which can be the same or different, are eachindependently hydrocarbons selected from aromatic chains having 6 to 10carbon atoms or alkylenes having 2 to 10 carbon atoms; and R¹³, R¹⁴,R¹⁵, and R¹⁶, each of which can be the same or different, are eachindependently hydrogen, hydrocarbons selected from aromatic chainshaving 6 to 10 carbon atoms, alkyls having 1 to 10 carbon atoms, orhydroxyalkyls of the following Chemical Formula 4:  —R¹⁷—OH  [ChemicalFormula 4] where R¹⁷ of the Chemical Formula 4 is a hydrocarbon selectedfrom aromatic chains having 6 to 10 carbon atoms or an alkylene having 1to 10 carbon atoms.
 10. A process for preparing a hydropolyoxyalkyleneoxyalkyl amine compound in accordance with claim 9, wherein thealkyleneoxide is alkyleneoxide having 2 to 5 carbon atoms.